Cathode for a secondary electrochemical cell

ABSTRACT

An electrochemical cell is disclosed which comprises an alkali metal anode, a molten salt electrolyte including that alkali metal in ionic form, and an improved cathode. The cathode composition comprises a transition metal sulfide such as FeS2, a particulate current collector, e.g. carbon black, electrolyte and a sulfide product, e.g. Li2S, of the cell reaction in excess of that produced by electrochemical reaction of the transition metal sulfide with the alkali metal in the discharge of the cell. Operation of the cell is performed by first electrocharging the cathode in series with the anode to convert the sulfide reaction product into a usable cathode reactant submerged in molten electrolyte.

United States Patent [1 1 Gay et al.

[451 Sept. 23, 1975 1 1 CATHODE FOR A SECONDARY ELECTROCHEMICAL CELL [75] Inventors: Eddie C. Gay, Park Forest; Fredric J. Martino, Dolton, both of 111.

[73] Assignee: The United States of America as represented by the United States Energy Research and Development Administration, Washington, DC.

[22] Filed: Jan. 18, 1974 [21] Appl. No.: 434,459

5/1972 Cairns et al 136/20 X Cairns et a1 1316/20 X Cairns ct al 136/6 LF [5 7] ABSTRACT An electrochemical cell is disclosed which comprises an alkali metal anode. a molten salt electrolyte including that alkali metal in ionic form, and an improved cathode. The cathode composition comprises a transition metal sulfide such as FeS a particulate current collector, e.g. carbon black, electrolyte and a sulfide product, e.g. Li S, of the cell reaction in excess of that produced by electrochemical reaction of the transition metal sulfide with the alkali metal in the discharge of the cell. Operation of the cell is performed by first electrocharging the cathode in series with the anode to convert the sulfide reaction product into a usable cathode reactant submerged in molten electrolyte.

10 Claims, 5 Drawing Figures HVERWGE POWER DEA/SIT); N

US Patent Sept. 23,1975 Sheet 1 of4 3,907,589

-'l g- /z /7- i I l l l 20 /0 60 8O PULSE DURATION, .560 (/.01/ 6ut-aff US Patent Sept. 23,1975 SheetZ of4 3,907,589

MG N6 A VY MQQQ M iuma Nm US Patent Sept. 23,1975 Sheet4 Of4 3,907,589

f aw 170A 7799 CATI-IODE FOR A SECONDARY ELECTROCHEMICAL CELL CONTRACTUAL ORIGIN OF THE INVENTION BACKGROUND OF THE INVENTION A This invention relates to secondary electrochemical cells and batteries of such cells thatcan be employed as power sources for electric automobilesor for the storage of energy generated during intervals of off-peak power consumption.

A substantial amount-of work has been done in the development of electrochemical cells and their electrodes. Thecells showing most promise employ alkali metal anodes such as lithium or sodium, molten salt electrolytes containing the alkali metal ions and cathode materials of Groups VIA and VIIA of the Periodic Chart, the chalcogens and halogens. Examples of such secondary cells and their various components are disclosed in US. Pat. No. 3,716,409 to Cairns et al., entitled =Cathodes for Secondary Electrochemical Power- P-roducing Cells, Feb. 13, i973; US. Pat. No. 3,666,560 to Cairns et al., entitled Electrochemical Power-Producing Cell, May 30, 1972; and US. Pat. No. 3,488,221 to I-Iiroshi Shimotake et al., Jan. 6, 1970; All of these patents are assigned to the assignee of the present application.

Many of the prior electrochemical cells designed to have high power densities have employed sulfur as the cathode reactant. When sulfur is used alone as the ac tive material in the cathode, it tends to escape from the electrode as a resultof' vaporization and dissolution into the electrolyte. Both of these effects can be sup pressed to some extent by the addition of various elements suchas arsenic, selenium or thallium. The use of these additives is more fully described in the assignees copendingapplication by Gay et al. entitled Second ary Electrochemical Power-Producing Cells Having Mixed Cathode Compositions, filed Sept. 28, 1973, Ser. No. 401,729.

Further reductions in sulfur activity and loss can be made through use'of metallic sulfides as the cathode material. For instance, electrochemical cells have been proposed which employ lithium as the anode reactant along with a transition metal sulfide such as FeS C05 C 5 NiS M08, or- CuS as the cathode reactant. (Etude Thermodynamique des' Generateurs a Electrode de Lithium, Entropie, No.. 40, pp. 24-34, JuilletAout I971, Caiola et al.) Other cathode reactants -that havebeen considered include FeS, Sb S As S- AS253 and P 8 Typical cathode reactions with the "above materials within a cell having a lithium metal reactant, that alkali metal is substituted for lithium in the anode reaction.

These transition metal sulfides and other sulfides are effective to maintain sulfurwithin, the cathode structure but in some instances they suffer from certain disadvantages as compared to elemental sulfur as a cathode reactant. For example, the lowerthermodynamic activity and greater molar equivalent weight of these compounds results in reduced cell voltage, capacity density and power density; Certain of these compounds, particularly iron pyrite, have been found difficult to form into an adherent mass with current collector materials. Furthermore, volume increases occurring with the cathode reaction can rupture anelectrode or cell housing and produce electrical shorts. As an example, the above reaction employing iron disulfide as a cathode reactant results in a theoretical volume increase of 2.6 to 1 compared to a volume increase of only 1.2 to l where elemental sulfur is the cathode reactant. In the operation of experimental cells known to the inventors with iron pyrite as a cathode reactant, volume increases in excess of 2.6 to 1 have been ob served.

Therefore, in view of these shortcomings of the prior art, it is an object of the present invention to provide a method for preparing a cathode composition including achalcogen reactant in. a form which will minimize reactant loss. a 1 it i v It is a further object of the present invention to provide a method of preparing a cathodeincluding a transition metal sulfide as a-reactant wherein cell voltage, capacity and power are maximized.

It is also an object to provide a novel cathode composition including a chalcogen reactant wherein the chalcogen is strongly retained within the cathode and the cathode expansion is minimized during discharge of the cell.

SUMMARY OF THE INVENTION.

In accordance with the present invention, a method is presented for preparing a high-temperature, electrochemical cell includinga transition metal sulfide as a cathode reactant," alkali metal asananode reactant and an electrolyte including ions of the alkali metal. The method comprises admixing the transition metal sulfide and the sulfide product of the cell reaction into a flocculent homogeneous mass with electrolyte and a particulate current collector. The mass is enclosed within a cathode structure and assembled with the electrolyte and anode as an electrochemical cell. The cell is heated to a temperature suffici'ent to melt the electrolyte, An electric current is applied from cathode to anode wherein the sulfide reaction product is electrolyzed the cathode to form additional cathode reactant other than the initial, transition metal sulfide. After thus charging the cell, it is then ready for use as a source of electrical voltage.

The invention also comprehends a novel cathode composition which includes in its initial state a transition metal sulfide and the sulfide reaction product of the cell reaction. The reaction product, e.g. Li S, permits formation of additional cathode reactant other than the transition metal sulfide within the cathode after the cell is brought to operating temperature and the electrolyte made molten. The sulfide reaction product is provided in sufficient quantity to provide a stoichiometric excess of sulfur as combined in the transition metal sulfide. In the FeS Li cell, for example, the total atomic sulfur concentration within the cathode is in excess of twice the total atomic concentration of iron. Where carbon or other particulate, electrically conducting material is included within the cathode as a current collector material, thepresence of lithium sulfide is of further benefit inwetting the surfaces of the current collector with electrolyte. 1 I

BRIEF DESCRIPTION OF THE DRAWINGS The presentinvention is illustrated in theaccompanying drawings wherein:

FIG. 1 is a schematic view of an experimental cell used to demonstrate the present invention;

FIG. 2 is a graph showing voltage v capacity density for cells 8-48 and 8-52. 1

FIG. 3 is a graph of voltage v capacity density for cell FIG. 4 is a graph of average power density v pulse duration for cells 8-50, 8-51 and S-52.

FIG.'5 is a graph showing voltage v capacity density for cell S-S'l. 1

DETAILED DESCRIPTION or THE; PREFERRED EMBODIMENT.

Referring to FIG. 1, an experimental secondary electrochemical cell 'is presented. The cell comprises a cathode 11 and an anode l3 separated and covered by a molten-electrolytic salt disposed within an alumina crucible "17. Electrical leads 1-0 and 12 extend from cathode 11 and anode 13 respectively. for connection to an electrical load (not shown). One suitable form of anode 13 includes a porous substrate of stainless steel impregnated with molten lithium metal. The stainless steelsubstrate can comprise a compacted and sintered mass of stainless steel fibers processed to provide the desired porosity, e.g. about 90%. As shown, the anode structureis enclosed within an expanded mesh 19 of molybdenum metal to act as a current collector and insure structural integrity. v

Cathode structure 11 includes a sealed graphite housing 21 with a window 23 of: porous fabric facing the anode structure. Window 23 can be of boron-nitrideQcalcium zirconate, yttria or other suitable porous fabric. The improved cathode material 25-of the present invention is placed within the inner chamber defined by housing 21 and window 23.

In practice, any cell design may be used with-th cathode material of the present invention; Thecell of FIG.- 1 merely represents an example of thetype cell used experimentally to test and-prove the operabilityof the invention; One practical cell design which could be used in'm'aking up electrochemical batteries for offpeak storage-of electrical power, as a power'source for an electric vehicle, or even as a small battery for implantation within a living being or animal is illustrated and completely described in the assignees copending patent application entitled Modular Electrochemical Cell to Walsh et al., filed Nov. 15, I973 Ser. No. 4l6,3l l.-'ln this modular cell design, the cathode material is enclosed within a porous fabric, possibly reinforced with a metallic mesh, and placed between two anode structures within a sealed, disk-shaped housing. Cathode material 25 is a blend of particulate reactant materials, a particulate current collector and a molten electrolyte forming a floccule'nt mass. A transition metal sulfide such as res C05,, 5,, M8 or M08 is selected as a cathode reactant. In addition to the transition metals, it is reasonable in view of the reference cited within the Background of the Invention to assume that a copper sulfide would also serve as a cathode reactant. r

- The current collector can be an electrically conductive material such as finely divided carbon black particles. Various alkali metal salts and mixtures of salts are well known as electrolyte materialsfor use in hightemperature cells; Eutectic compositions of LiF'I .i-

'Cl-KCI and -LiCl'KCl have served well in numerous experimental'electrochemical cells.

The inventors have'foiind that, by including critical concentrations of the alkali metal sulfide that is the reactionproduct of the cell, e.g lithium sulfidei-within the cathode mixt'ure, beneficial and unexpected'results are produced; sufficient lithium -sulfide is included within'thecathode material to provide a total molar,

that is atomic, concentration of sulfur in stoichiometric excess of the total atomic concentration of iron or other transition metal. In the case of iron pyrite,'FeS

the atomic concentration of sulfur -is more than twice the'atomic concentration of iron within the cathode material. --'&= 1 I As shown above, elemental iron is one-reaction productwithin the iron pyrite and lithium-electrochemical cell. In some instances,- iron "is included'asa current collector material within'the cathode composition, but in accordance with a preferredembodiment of the invention, sufficient Li S is also included to" provide a stoichiometric excess of sulfur in respect to the iron. The sulfide reaction product of the cell, Les; is ineluded within the cathode material-for 'amumber of "reasons. It is found that-even a small concentr'ationof lithium sulfide, e.g. about 2 weight percent, is sufficient to enhance the wetting of carbon-black with the electrolyte-and thereby enhance the electricalconductivity between the iron pyrite and carbon black particles. Ad-

ditionalquantities of lithium sulfide within the initial cathode composition, for instanceof about 25 weight percent, can be electrolyzed on charging the electrochemical cell to form additional cathode reactant.

Where a stoichiometric excess of sulfur in respect to iron is provided, the additional" cathode reactant-appears to be in a form havinga higher activity than that of iron -disulfide. The additional cathode; reactant, other than iron-'disulfide, could be elemental sulfur trapped within'the composition or a sulfur compound. It is evidenced by high sulfur utilization and power den sity, as will be seen on consideringthe Examples below. This procedure of-producing. additional cathode reac-' tant after the cell is assembled is of'considerable adv'antage over prior techniques in which elemental sulfur is included within the initial cathode composition; On bringing-the electrolytic 'cell up to operating temperatures, sulfur vapor easily escapes from these previous cells through interstices within" the solid electrolyte Prior to fusion. I I

In still another beneficial effect of the present invention, a formidable difficulty with theiron pyrite cathode material is overcome'. The basic iron pyrite reaction with lithium metal incurs a'theoretical volume increase of approximately 2.6 to 1. In theoperation of experimental 'cells having iron pyrite electrodes, sufficient electrolyte or void space has been included in the cathode to accommodate an expansion of this magnitude, but distortion 'stilloccurred; indicating even larger than theoretical expansion. In cells having iron pyrite cathodes prepared in accordance with the invention, that is with excess Li S in the composition, the amount of expansion has been noticeably reduced. One

On assembling the cathode composition within the cathode chamber of an electrolytic cell, capacity densities greater than 0.3 amp-hr/cm were measured at 0.1 amp/cm to a 1.0 volt cutoff. This corresponds to a spepossible explanation is that the additional cathode re- 5 cific capacity of about 0.5 amp-hr/cm of sulfur elecactant produced by electrocharging the excess Li S retrode volume. However, in spite of these promising reacts w1th a volume change more in accord with that insults, a substantial volume increase was noted in the curred by the sulfur-lithium reaction of only approxicathode materials. mately 1 to 1.2.

The following examples are presented to illustrate the novel cathode com osition and method of the resp P EXAMPLE 11 c611 s-sz ent 1nvent1on. Table l g1ven below summarizes the physical characteristics of the cells presented in Exam- A Somewhat larger electrochemical Cell With Cathples l-IV. ode composition substantially the same as that shown TABLE I Example I II III IV Cell NO." S48 s-52 s-50 S--5l Lithium Electrode Area, cm 22.8 167.2 12.9 12.9 Li or Li alloy, g 10.2 19.9" 2.5" 2.5 Electrolyte LiCl-KCI LiF-LiCl-KCl LiF-LiCl-KCI LiF-LiCl-KC] Sulfur Electrode Area. cm 16.5 50.8 5.1 5.1 Active Material FeS FeS FeS Li S FeS. Li S Weight, g 11.6 40.0 5.0 5.4 Comp.. wt "/1 Fcs 60.0 60.0 33.5 23.7 L1 8 2.2 2.2 26.6 34.5 Electrolyte 29.3 29.3 32.5 34.2 Carbon Black 7.0 7.0 6.6 6.9 Fe 1.5 1.5 0.8 0.7 Equivalents. S

Fes 11.6 40.0 2.21 2.1 1.1 5 0.56 1.9 2.9 4.05 Fe (as FeS- 0.60 2.1 0.14 0.13 Theoretical Capacity Density, A-hr/cm'- 0.67 0.44 0.60 0.65

"The interclectrudc distance for these cells was 0.6 cm, the temperature range was 380 to 400C.; :1 boron nitride sheath was used for all of the cells.

"These anodes contained about wt copper and 75 wt "/1 lithium impregnated within a porous metallic substrate.

EXAMPLE I (Cell 8-48) A little more than 11 grams of cathode constituents are blended together to form a flocculent: mass of cathode material at the cell operating temperature of about 400C. The cathode composition comprises about 60 w/o FeS 2.2 w/o Li S, 29.3 w/o electrolyte (Li- Cl-KCl), 7 w/o carbon black and 1.5 w/o of particulate iron filings. The amount of iron is more or less stoichiometrically equivalent to the amount of sulfur within L1 5, such that on charging this cell, all of the sulfur can be combined to form Fe S. The iron pyrite, lithium sulfide and iron filings are all commercial-grade products and, in some instances, contained inert impurities. For example, up to 15 w/o silicon oxide was noted in the iron pyrite samples. Particle sizes of about 0.015 pm to 0.2 mm have been found to be sufficient for use in the cathode composition. The carbon black is a finely divided commercial product of about 0.015 ,u.m particle size. This carbon black material is of low porosity, that is, individual carbon black particles have low surface areas in respect to volume of the particles.

The cell constituents are thoroughly blended together within a vitreous carbon crucible at about 400C. The resulting mixture appeared as a flocculent but homogeneous mass with intimate wetting of both the iron pyrite and carbon black particles with the electrolyte. The mixture is in contrast to previous cathode compositions containing no lithium sulfide in which separation of the iron pyrite and carbon black appeared.

in Example I was prepared. As in Example I, the cell size and characteristics are set forth in Table I. This cell, cell S-52, employed a cathode structure made of a molybdenum mesh basket enclosed with boron nitride cloth. A coiled molybdenum mesh current collector was placed within the basket and in electrical contact with the cathode composition. The electrode assembly was covered with boron nitride cloth and compressed between two molybdenum nuts. The cathode as thus prepared was assembled within a sealed electrochemical cell containing an anode as described above, except that approximately 25 w/o copper was blended into solution with thelithium metal. The initial operation of the cell wasinterrupted by a short circuit between the electrodes caused by expansion of the cathode composition. After the electrical short was cleared up, the cell was operated for hours and 21 cycles.

The performance of cells S-48 and 8-52 as described in Examples I and 11 above is further illustrated in FIG. 2 which shows a plot of cell voltage versus capacity density over the discharge portion of the cell cycle for each of the cells.

EXAMPLE III (Cell S-50) Cell S-50 was prepared in much the same manner as cell S48 and its characteristics are also shown in Table I. This cell includes a substantial concentration of lith- 7 ium sulfide within the initial cathode composition thus providing a considerable stoichiometric excess of sulfur over that required to form iron disulfide. I s I This cell operated for over 900 hours and. 90 cycles.

manner as 1 0611 3-50 except that a larger concentration of lithium sulfide is included in the cathode composition. A short-time power density of 2.8 watts per cm was obtained which is greater than that of the previous The cell voltage as a function of capacity density at 5 cells. Also apower density greater than 1 watt per cm three discharge cycles and current densities are sliown was sustained for up to 55 seconds. The power density in FIG. 3. Initial voltages as thus shown are somewhat of cell 5-51 is shown in FIG. 4 as well as those of cells higher than those shown in FIG. 2 for cells 48 and 52, 8-50 and 8-52. but more important this cell demonstrated a much The operation of cell S-Sl continued for 770 hours higher power density than the previous cells having 10 and 53 cycles, .but after about 500 hours of operation only small quantities of Li s in the initial-cathode comthecapacity density dropped to about one-half its origiposition. Power densities even for a short time are of nal value at 1 volt cutoff. In FIG. 5 this rapid drop in importance in evaluating a cell or battery for use as a capacity density is illustrated for discharge cycles 7, 17 power supply within an electric automobile or other veand 44. SillCE the total equivalents Of sulfur within the hicle. Shortime power densities as much as l .4 watts Cathode Of C ll 3-51 is almost three times that required per i h power d i i f 6 watt to combine with the iron as iron disulfide (see Table I), tained for up to 50 seconds were obtained from cell 50. substantial amounts of free elemental sulfur were possi- This is in contrast to short-time power densities of only bly produced during electrocharging'Loss of this reac- O.5 watt per cm obtained in cell 8-52 and ell 5-48, A tant into the electrolyte could account for the decrease comparison of power densities is illustrated in FIG. 4. 20 in p y- For this reason. t is f importance to limit Additional detailed performance data for cell 5-50 are the amount of sulfur introduced as product of the sell given b lo i T bl [1 reaction (Li S) to about twice that required to combine TABLE II PERFORMANCE DATA FOR CELL 3-50" Discharge Charge Discharge Percent of Average Current Current Capacity Theor. Cap. Discharge Watt-Hr Cycle Density, Density, Density, Density, Voltage Efficiency No. A/cm A/cm" A/cm V 4 "The charge and discharge cutoff voltages were 2.37 V and 1.0 V. respectively.

It can be seen from Table II that at least some of the with iron in FeS Such a concentration was included in sulfur introduced into the cathode composition as LiS 40 cell -50 of Example III and, as was discussed above reis converted into a cathode reactant. The theoretical specting Table II, the cell capacity had actually incapacity density employed in computing the fifth colcreased slightly between the third and seventyfirst cyumn of Table Ilis based on reaction of all of the sulfur I cles. in both the FeS and in the U 5. In Example III the It is also observed in both cells 5-50 and 8-5] that relamount of sulfur required to combine with all of the atively small volume increases were incurred after the iron as FeS is about one half the total sulfur in the initial discharge with resulting higher specific capacicathode composition. (See Table I for equivalents of ties (amp hours per cm than for cells 8-48 and 8-52. sulfur.) Phrased differently, the atomic concentration The smaller volume increases are attributed to the of lf in thi ath de i about f ur tim th at mi higher lithium sulfide concentration within the initial concentration of iron. Thus, a reaction of all the FeS- Cath de C0mposition. t f Li S i any one l hi h i most i b Although the invention has been described with reble, would provide a pcrcentage of theoretical capacity I spect to a fW reactant materials, It be clear that density of only 50%, In iew of the above percentages various other reactants within bOth the anode and the near and in excess of 50%, it is only reasonable to -conv CathQde can be p y For p Various other clude that a cathode reactant other than FeS is present alkali metals Such as Sodium or an alloy of lithium can within the charged cell of this example; be used within the anode. Potential cathode materials Another aspect of cell 50 performance shown in otherthan II'OII disulfide include those listed herein- Table II is the reproducible capacity density with cy- I Qbov. In accordance with theinvention, the reaction cling. Cycles 3, 21 and 71, all having approximately the 6 product of those various transition metal sulfides with same charge and discharge currents, show a slight int I lithium'cation or other alkali metal cation as produced crease in capacity with cycling. Intervening cycles in the cell reaction is blended into the initial cathode shown in the table were either charged or discharged composition at a sufficient atomic concentration to at increased currents which accounts for their dcprovide a stoichiometric excess of sulfur in respect to creased capacity densities. that transition metal within the cathode.

EXAMPLE 1v (Cell 's-sl Characteristics of this cell are also given above in Table l. The cell is constructed essentially in the same lt canbe seen that the present invention provides a novel cathode composition including a metallic sulfide v as a cathode reactant intermixed with a reaction product of that sulfide and the alkali metal employed as the cells anode reactant. Through use of this composition,

cathode reactant including sulfur can be entrapped within the cathode material without incurring sulfur losses that would otherwise result from sulfur vaporization prior to fusion of the electrolyte. It is also found that this reaction product, e.g. lithium sulfide, enhances the wetting of carbon-current-collector mate rial within the cathode composition and thereby decreases the cell resistance.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as folreaction product of said alkali metal and said transition metal sulfide, the total atomic concentration of sulfur combined with said transition metal and said alkali metal reactant within said cathode being in stoichio- 'metric excess of the total atomic concentration of said transition metal.

2. The improved cathode composition of claim 1 comprising FeS and at least 2 w/o U 8.

3. The improved cathode composition of claim 2 wherein the total atomic concentration of sulfur is in excess of twice the total atomic concentration of iron in saidcathode.

4. The improved cathode composition of claim 3 wherein the atomic concentration of sulfur is about four times they atomic concentration of iron and the atom equivalents of sulfur in said cathode are about twice that required to combine with iron as iron disul- 5. The electrochemical cell of claim 4 wherein said cathode comprises by weight about 33% FeS- 27%, Li S, 33% electrolyte and 7% carbon black.

6. A method of preparing a cathode for use in a secondary electrochemical cell wherein said cell includes a cathode structure with inner chamber, an anode with an alkali metal reactant, and an electrolyte including ions of said alkali metal in contact with both of said electrodes, the improvement comprising:

a. blending particulate transition metal sulfide, sulfide reaction product of said anode reactant and said transition metal sulfide, molten electrolyte and particles of electrically conductive material to form a cathode composition; and

b. assembling said cathode composition into said cathode structure of said electrochemical cell for use as a source of electrical power.

7. The method of claim 6 wherein said electrochemical cell is heated to an operating temperature at which said cathode composition is submerged in molten electrolyte; and electrically charged to convert said sulfide reaction product into cathode reactant other than said transition metal sulfide at said operating temperature.

8. The method according to claim 7 wherein said sulfide reaction product is Li S, said transition metal sulfide is FeS and said electrolyte comprises a eutectic.

composition of LiF-LiCl-KC] having a melting point of about 350C., said Li S is included within said cathode composition in an amount to provide a stoichiometric excess of sulfide within said cathode to that needed to combine as FeS 9. The method according to claim 7 wherein said cathode composition is formed by blending powders of lithium sulfide and iron disulfide with molten LiFLi- ClKCl electrolyte in a weight proportion of about 27%, 33% and 33%, respectively, along with about 7 w/o carbon black.

10. The method of claim 7 wherein said cathode composition is assembled in said cell within a cathode enclosure having a window of porous fabric facing said anode and exposed to said electrolyte. 

1. IN A SECONDARY ELECTROCHEMICAL CELL INCLUDING AN ALKALI METAL REACTANT IN THE ANODE, A CATHODE COMPOSITION INCLUDING A CHALCOGEN REACTANT IN THE CATHODE AND AN ELECTROLYTE CONTANING IONS OF SAID ALKALI METAL, THE IMPROVEMENT WHEREIN SAID CATHODE COMPOSITION COMORISES: AT LEAST ONE TRANSITION METAL SULFIDE AND A SULFIDE REACTION PRODUCT OF SAID ALKALI METAL AND SAID TRANSITION METAL SUFIDE, THE TOTAL ATOMIC CONCENTRATION OF SULFUR COMBINED WITH SAID TRANSITION METAL AND SAID ALKALI METAL REACTANT WITHIN SAID CATHODE BEING IN IN STOICHIOMETRIC EXCESS OF THE TOTAL ATOMIC CONCENTRATION OF SAID TRANSISTION METAL.
 2. The improved cathode composition of claim 1 comprising FeS2 and at least 2 w/o Li2S.
 3. The improved cathode composition of claim 2 wherein the total atomic concentration of sulfur is in excess of twice the total atomic concentration of iron in said cathode.
 4. The improved cathode composition of claim 3 wherein the atomic concentration of sulfur is about four times the atomic concentration of iron and the atom equivalents of sulfur in said cathode are about twice that required to combine with iron as iron disulfide.
 5. The electrochemical cell of claim 4 wherein said cathode comprises by weight about 33% FeS2, 27%, Li2S, 33% electrolyte and 7% carbon black.
 6. A METHOD OF PREPARING A CATHODE FOR USE IN A SECONDARY ELECTROCHEMICAL CELL WHERREIN SAID CELL INCLUDES A CATHODE STRUCTURE WITH INNER CHAMBER, AN ANODE WITH AN ALKALI METAL REACTANT, AND AN ELECTROLYTE INCLUDING IONS OF SAID ALKALI METAL IN CONTACT WITH BOTH OF SAID ELECTRODES, THE IMPROVEMENT COMPRISING: A. BLEDING PARTICULATE TRANSITION METAL SULFIDE, SULFIDE REACTION PRODUCT OF SAID ANODE REACTANT AND SAID TRANSITION METAL SULFIE, MOLTEN ELECTROLYTE AND PARTICLES OF ELECTRICALLY CONDUCTIVE MATERIAL TO FORM ACATHODE COMPOSITION: AND B. ASSEMBLING SAID CATHODE COMPOSITION INTO SAID CATHODE STRUCTURE OF SAID ELECTROCHEMICAL CELL FOR USE AS A SOURCE OF ELECTRICAL POWDER.
 7. The method of claim 6 wherein said electrochemical cell is heated to an operating temperature at which said cathode composition is submerged in molten electrolyte; and electrically charged to convert said sulfide reaction product into cathode reactant other than said transition metal sulfide at said operating temperature.
 8. The method according to claim 7 wherein said sulfide reaction product is Li2S, said transition metal sulfide is FeS2 and said electrolyte comprises a eutectic composition of LiF-LiCl-KCl having a melting point of about 350*C., said Li2S is included within said cathode composition in an amount to provide a stoichiometric excess of sulfide within said cathode to that needed to combine as FeS2.
 9. The method according to claim 7 wherein said cathode composition is formed by blending powders of lithium sulfide and iron disulfide with molten LiF-LiCl-KCl electrolyte in a weight proportion of about 27%, 33% and 33%, respectively, along with about 7 w/o carbon black.
 10. The method of claim 7 wherein said cathode composition is assembled in said cell within a cathode enclosure having a window of porous fabric facing said anode and exposed to said electrolyte. 